Process for rendering fibrous textile materials fast to slipping



Patented Dec. 4, 1945 PROCESS FOR RENDEBJNG FIBBOUS TEX- TILE MATERIALS FAST TO SLIPPING om Albrecht, Nelle-welflneal Basel, Swltserland, asslgnor to the Swiss firm of Society of Chemical Industry in Basic, Basel, Switzerland No Application February 2, 1942 Serial 429,337. In Switzerland February 12,

7 Claims. (Cl. s-uc.2.)

, It has been found that textile fabrics which tend to slip-that is, in which the warp and weft threads are readily displaced when subjected to mechanical stress-can be made fast to slipping by treating them with solutions or dispersions of compounds of the general formula R-CHz-Rr in which R is the radical of a compound which is either resin-like or may be converted into a resin and which contains at least one hydroxyaryl group and R1 is a radical, preferably the isothiourea radical in salt form, which imparts or increases solubility in water and which contains at least one basic nitrogen atom, the radical R1 being united to a nuclear carbon atom of the radical R by means of the OKs-bridge, drying them and, if desired, treating them at raised temperature. Compounds which are resinous or may easily be converted into resinous compounds, for instance, by condensing with formaldehyde that is to say, fibres which no longer slip. In otherwords, the fact that a basic watersolubilizlng group is connected througha methylene bridge with a hydroxy aryl radical; is critical for the efliciency of the products used. the methylene bridge causing-the decomposability 'of'the products and the cationactivity beingresponsible for the high efliciency of low concentrations, as

will be shown at the end of the introduction,

The compounds to be used in carrying out the presentinvention are more or less cationactlve;

according to the nature of the parent materials used in the manufacture, and cause an improveare hereinafter designated as resin forming compounds. The expression solution is hereinafter with aqueous solutions which contain 0.25 to 1% of compounds of the composition described above, it is then squeezed or hydroextracted and dried, for example, at 105-110 C. It may be advisable then to heatthe fibrous material thus obtained for a shorter or longer period at a still higher temperature, for example, at a temperature between 115 and 150 6;, but preferably at a temperature lower than 180 C. Temperatures above 180 C. are not to be recommended, as the textile flbresmay be damaged at still higher tem- It is very probable that, during the drying process, especially at raised temperatures, a decomposition of the products used in the invention takes place. Since the methylene bridge -CH: connecting the hydroxy aryl radical ment in the anti-slip properties of the fabric even when used in comparatively low concentrations, the handle of the fabric, in g neral, not being unfavourably influenced thereby. Further, they improve the fastness to water of dyeings, in many cases, provided that fibrous materials are treated which have been dyed with dyestuffs containing sulfonic acid groups.

The products mentioned may be used either alone or in combination with other products, for

V eral formula example, salts of weak acids.

As compounds of the general formula RdO-CH2R1 m which R2 represents a substituted or unsubstituted cycloaliphatic, cycloaliphatic-aliphatic or aromatic-aliphaticradical, a represents a hyd xyaryl radical, which mayalso contain other substituents, and R1 has the meaning given above.

As compounds of the general formula I Ra-a-CE-R in which R3 represents a cycloaliphatic or cycloof the aforesaid products with the water-solubilaliphatic-aliphatic radical, and in which a and R1 have the meanings given above, compounds may be used, for instance, which are derived from the known-particularly the resinlike-addition products, containing phenolic hydroml groups, of aromatic hydroxy compounds, for example, of phenol, alkylated phenols, such as cre-.

sol and the like, with compounds of the terpenic series, especially terpene alcohols or We hydrocarbons, such as dipentene, as well as with As compounds of the above-mentioned formula RzoCHz-Ri, in which Rzrepresents an arcmatic-aliphatic radical and,a and R1 have the meanings already given, products may be used which are derived, for example, from 1:1-di-(phydroxyphenyl) ethane, I dihydroxydiphenylmethane, dihydroxydiphenyl-dimethyl-methane, as well as from condensation products of formaldehyde with aromatic hydroxy compounds, for example, from phenol-formaldehyde condensation products, which are still soluble in organic solvents and are obta ned in the presence of acid or alkaline reacting. substances. I

Water-soluble compounds derived from the above mentioned condensation products of hydroxy compounds of the benzene series with terpenic alcohols, terpenic hydrocarbons. resinous acids occurring in nature and formaldehyde correspond to the formula R2l-CHa-R1 wherein R: is a substituent the carbon chain of which consists of at least one open'chain with 1 to 3 carbon atoms and of .at least one six-membered carbon ring, a is an arylene radical of the henzene series containing at least one hydroxy group andRi has the meaning given above. As is well known, compoundsof the terpenic series and resinous acids occurring in nature contain sixmembered carbon rings towhich side chains with l to 3 carbon atoms are fixed; moreover these terpenic and resinous compounds contain carbon chains which may be regarded as being built up of isoprene radicals. Condensation products of hydroxy compounds of the benzene series with formaldehyde also contain carbon chains consisting of at least one open carbon chain with 1 to 3 carbon atoms and of at least one six-membered carbon ring, since, as is well known, the benzene nuclei of these condensation products are connected with one anotherthrough '-CH2-- bridges.

Suitable products derived from the above mentioned formaldehyde condensation products are, for instance, those which correspond to the formula Ra-'CH:--Ri wherein Ra is a radical of a product obtained by condensing ahydroxyaryl compound of the benzene series, such as phenol, with formaldehyde in the presence of an acid. a nuclear carbon atom of the said radical Ra bei connected with the methylene group- They react as if the atom grouping were present in the molecule. Therefore, a substitution, if any, takes place at the sulfur atom, isothiourea radicals of the formula being introduced. Examples of compounds con- 1 taining isothiourea radicals are the salts of the products of the formula (in which R: represents an aromatic-aliphatic radical and R1 an isothiourea radical in salt form) which are to be used in carrying out the invention by treating an aromatic hydroxy compound, such as phenol o resorcinol, with formaldehyde and thiourea and with an acid, especially hydrochloric acid, for example, by heating to 100 0., if desired, in the presence of solvents. In

such circumstances nuclear condensations take place, by means of which at'least two hydroxylaryl radicals become united together by memo! a methylene bridge.

The products used in the invention are cationactive. This is the reason why they are easily absorbed by textile fibre such as cellulose fibres.

Therefore the class of cationactive substances is scope.

- Example 1 a solution of'0.25 per cent. strength of the formate of an isothiourea derivative (prepared by the action of the thiourea, formaldehyde and hydrochloric acid on the phenol-like addition.

product of phenol and dipentene) is prepared and is used to impregnate a viscose rayon fabric which has a tendency to slip, that is to say, of which the warp and weft threads are readily displaced by mechanical strain. The impregnated fabric is then squeezed and dried on the calender at about l05-l10 0., when it will be found to be appreciably faster to slipping than an untreated portion of the material.

The formate solution used above can be prepared as follows: 4.6 parts of the known phenollike addition product of phenol and dipentene are finely powdered and are added to a solution of3partsofthioureainami1tureof33parts of formaldehyde solution of 36.8 per cent.'

strength and 3.3 parts of volume of hydrochloric acid of approximately 12-01 strength. This reaction mixture is stirred for about 24 hours one boiling water bath. After cooling, the reaction product, which is a brittle solid, is pulverized and, is heated to 50 C. with about 100 parts by volume of very dilute'hydrochloric acid. The portion of the reaction product which remains undissolved is filtered oil and dried at a low temperature. In order to convert it' into the formate, the compound thus obtained is dissolved in warm alcohol, and the solution is poured into water which has been acidified with formic acid. The inmate corresponds to the formula Example 2 Example 3 A solution of 1 per cent. strength of the isothiourea hydrochloride which is obtained by the reaction of thiourea, formaldehyde and hydrochloric acid on 1:1-di- (p-hydroxyphen'yl) -ethane is prepared and usedto impregnate a viscose rayon fabric which has a tendency to slip, which is then squeezed. After drying it on the calender at about IDS-110 0., the treated fabric will be found to be much faster to slipping than the untreated.

The isothiourea hydrochloride used can be prepared as follows:

5.3 parts of finely powdered 1' :1-di-(p-hydroxyphenyl) -ethane are stirred with 3.8 parts of finely powdered thio'urea, 3.8 parts by volume of formaldehyde solution of 39.9 per cent. strength by volume and 4.1 parts by volume of 12.2-n-hydrochloric acid for 24 hours in a boiling water bath. The reaction product is separated after cooling,

' when it is twice boiled up with acetone and then.

' after decanting the acetone, freed from remain- A solution of 0.5 per cent. strength of an isothiourea salt, which is obtainable by reaction of thiourea hydrochloride and formaldehyde and a condensation product of colophony-with phenol,

' prepared in known manner, is prepared and used to impregnate a viscose rayon fabric which has a, tendency to slip. The fabric is then squeezed and, after drying on the calender at about 105-110" C., will be found to be appreciably faster to slipping than the original untreated material.

The isothiourea salt can be prepared as foltrated formic acid are added to the clear reaction solution thus obtained, which is then poured hot into about 100 parts by volume of water, the undissolved portions then being removed by fliterlng. The isothiourea salt which is obtained from.v the filtrate by evaporation is a powder which, when dissolved in alcohol, gives a clear. foaming solution on addition of water, and which corresponds to the formula wherein a: is a radical or colophony. In a similar manner the corresponding derivative of the condensation product of fl naphthol with colophpny may be used. Further, corresponding products containing an allyl isothiourea radical instead of theisothiourea radical may be used for rendering textiles fast to slipping.

ing solvent at low temperature. The isothiourea hydrochloride thus obtained, a pale yellow, brittle mass, after dissolving in alcohol gives an opalescent solution when diluted with water.

Example 4 An aqueous solution of l per cent. strength is prepared from the condensation product obtained by the reaction of thiourea, formaldehyde and hydrochloric acid on phenol and is used to impregnate a viscose rayon fabric which has a tendency to slip. The fabric is squeezed and dried on the calender at about 105-110 0., when it will be found to be much faster to slipping than the untreated'material.

The condensation product used can be obtained asfollows: I

94.parts of phenol are stirred with '76 parts of thiourea, 75 parts of formaldehyde solution of 39.9 per cent. strength by volume and 82 parts by volume of 12.2-n hydrochloric acid for 20 hours in a boiling water bath. The unchanged phenol is removed from the clear solution thus obtained by means of steam. The aqueou solution which is formed by the steam distillation-if necessary, after further addition of water-is poured oil the lower layer of reslnous matter, and

temperature. The condensation product thus obtained is a colourless, solid mass which is readily dissolved by water to form a clear solution, and which corresponds to the formula wherein R: is a radical of the product obtained by condensing phenol with formaldehyde in the presence of hydrochloric acid.

In a similar manner the corresponding product containing an ally] isothiourea radical instead of the isothiourea radical may be used for rendering textiles fast to slipping.

What I claim is:

1. Process for rendering fibrous textile material fast to slipping which comprises impregnatm the material with a solution containing a compound of the general formulawherein R: is a substituent the carbon chain or which consists of at least one open chain with l to 3 carbon atoms and of at least one six-membered carbon ring the carbon chain of the said substituent R: being built up of isoprene radicals, a is an aryiene radical or the benzene series containing at least one hydroxy group, and wherein R1 is an isothiourea radical in salt form, and then drying the impregnated material,

2. Process for rendering fibrous textilematerial last to slipping which comprises impregnating the material with a solution containing a compound of the general formula wherein R: is a radical of the terpenic series, a is an arylene radical of the benzene series containing at least one hydroxy group, and wherein R1 is an isothiourea radical in salt form, and then drying the impregnated material.

3. Process for rendering fibrous textile material fast to slipping which comprises impregnating the material with a solution containing a compound of the general formula wherein R: is a'radicai of dipentene, a is an arylene radical of the benzene series containing at least one hydroxy group and wherein R1 is an isothiourea radical in salt form, and then drying the impregnated material.

4. Process for rendering fibrous textile material fast to slipping which comprise; impregnating the material with a solution containing a salt of a compound of the formula wherein R: is a radical of dipentene, then drying Ra-a-CHz-Rr wherein R: is a radical of a resinous acid occurring in nature, a is an arylene radical of the benzene series containing at least one hydroxy group, and wherein R1 is an isothiourea radical in salt form, and then drying the impregnated material.

6. Process for-rendering fibrous textile material fast to slipping which comprises impregnating the material with a solution containing a compound of the general formula R:GCHa-R1 wherein R: is a radical of colophony, a is an andene radical or the benzene series containing at least one hydroxy group, and wherein R1 is an 25 isothiourea. radical in salt form,,and then drying the impregnated material.

'1. Process for rendering fibrous textile material fast to slipping which comprises impregnatingthematerialwithasolutioncontainingnsalt m of a compound of the formula mthaulilo'c.

the impregnated material, and subjecting the treatedmaterialtoaheatingtreatment atlm 

